Mechanistic Insights into Enhanced Hydrogen Evolution of CrOx/Rh Nanoparticles for Photocatalytic Water Splitting

• Published in: Chemistry : a European journal Vol. 29; no. 24; pp. e202204058 - n/a
• Main Authors: Higashi, Tomohiro, Seki, Kazuhiko, Sasaki, Yutaka, Pihosh, Yuriy, Nandal, Vikas, Nakabayashi, Mamiko, Shibata, Naoya, Domen, Kazunari
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 25.04.2023
• Subjects: Chemistry; Chromium; chromium oxide; electrocatalyst; Electron transfer; Fluorine; hydrogen evolution; Hydrogen evolution reactions; Nanoparticles; photocatalyst; Protons; rhodium nanoparticle; Splitting; Substrates; Tin; Tin oxide; Tin oxides; Water splitting
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202204058

The hydrogen evolution reaction (HER) of Rh nanoparticles (RhNP) coated with an ultrathin layer of Cr‐oxides (CrOx) was investigated as a model electrode for the Cr2O3/Rh‐metal core‐shell‐type cocatalyst system for photocatalytic water splitting. The CrOx layer was electrodeposited over RhNP on a transparent conductive fluorine‐doped tin oxide (FTO) substrate. The CrOx layer on RhNP facilitates the electron transfer process at the CrOx/RhNP interface, leading to the increased current density for the HER. Impedance spectroscopic analysis revealed that the CrOx layer transferred protons via the hopping mechanism to the RhNP surface for HER. In addition, CrOx restricted electron transfer from the FTO to the electrolyte and/or RhNP and suppressed the backward reaction by limiting oxygen migration. This study clarifies the crucial role of the ultrathin CrOx layer on nanoparticulate cocatalysts and provides a cocatalyst design strategy for realizing efficient photocatalytic water splitting. Hydrogen evolution reaction (HER) on Rh nanoparticles (RhNP) was investigated as a model cocatalyst system for photocatalytic water splitting. A 2‐nm‐thick ultrathin CrOx layer on RhNP (CrOx/RhNP) significantly improves HER activity. DC and AC electrochemical measurements revealed that a CrOx/RhNP facilitates the electron transfer process on HER, and H+ reaches the RhNP surface via the H+‐hopping process inside the CrOx layer.